Pesticidal triazinyl azides



United States Patent ABSTRACT OF THE DISCLOSURE Compounds of the general formula A, Bl ps wherein R represents a hydrogen atom, a halogen atom, the azide radical, an aliphatic radical containing up to 18 carbon atoms, the group CN, ACN or -ZX (wherein Z stands for oxygen or sulfur and X for an unsubstituted aliphatic radical containing up to 18 carbon atoms, or a S-membered to 7-rnembered, preferably a G-membered cycloaliphatic radical), R has the same meaning as R or the group (wherein A stands for an unsubstituted or substituted aliphatic radical containing up to 18 carbon atoms, a-

cycloaliphatic radical made up from 3 to 12 members, a lower alkoxyalkyl, hydroxyalkyl, cyanoalkyl, or alkylthioalkyl radical and A stands for a hydrogen atom or has the same meaning as A or A +A together with the nitrogen atom represent a S-membered to 7- membered, preferably a S-membered heterocyclic radical) are pesticidally active, particularly as herbicides and microbicides.

The present invention provides a pesticidal preparation, especially a herbicidal or microbicidal preparation, which comprises as active substance a compound of the general formula A El yn,

wherein R represents a hydrogen atom, an aliphatic radical containing up to 18 carbon atoms, the group -CN, -SCN or ZX (wherein Z stands for oxygen or sulfur and X for an unsubstituted or substituted aliphatic radical containing up to 18 carbon atoms, or a S-membered to 7-membered, preferably a G-membered cycloaliphatic rad- 3,415,827 Patented Dec. 10, 1968 ical), R has the same meaning as R or represents an azide radical, a halogen atom or the group (wherein A stands for an unsubstituted or substituted aliphatic radical containing up to 18 carbon atoms, a cycloaliphatic radical made up from 3 to 12 members, a lower alkoxyalkyl, hydroxyalkyl, cyanoalkyl or alkylthioalkyl radical and A stands for a hydrogen atom or has the same meaning as A or A i-A together with the nitrogen atom represent a S-membered to 7-membered, preferably a S-membered heterocyclic radical) together with a suitable carrier. There may also be present, in the preparations, one or more of the following additives: a solvent, a diluent, a dispersant, an adhesive and/or another pesticide, especially a herbicide and a. fungicide.

The present invention provides especially those preparations of the kind defined above which contain as active substance a compound of the general formula A, El n,

wherein R represents a lower alkyl radical or the group ZX (wherein Z stands for an oxygen or a sulfur atom and X for an unsaturated or saturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, a lower alkoxy alkyl or chloralkyl radical or a 6-membered cycloaliphatic radical which may be substituted by lower alkylene or alkyl groups), R has the same meaning as R or represents a halogen atom, especially a fluorine, chlorine or bromine atom, an azide radical or the group (III) wherein A represents an alkyl or alkenyl radical with up to 18 carbon atoms or a 3- to IZ-membered cycloaliphatic N N B s,

wherein X represents an alkyl or alkenyl radical contain ing up to 5 carbon atoms, preferably the methyl group, and R stands for the group Ar N If; A E

wherein X represents a saturated or unsaturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, or a lower alkoxyalkyl or chloralkyl radical or a cyclohexyl radical or an alkylene-cyclohexy-alkyl radical, and R represents the azide radical or the group wherein A stands for a saturated or unsaturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, a lower alkoxyalkyl radical or a cyclohexyl radical, and A for a hydrogen atom or a lower alkyl radical.

Preparations having a particularly good herbicidal effect are those containing the compounds of the following general formula wherein R represents a lower alkyl, a lower alkoxyalkyl or the cyclohexyl group, and X stands for a chlorine atom or the group CH S or CH O- or the azide radical. Among these compounds, the following are distinguished by their special potency:

and

Na l

The new compounds of the general Formula I can be prepared by methods know per se, for example by reacting a compound of the general formula wherein R and R have the same meanings as in the above general Formula I and X represents a halogen atom or a quaternary ammonium group-with an alkali metal azide, for example NaN preferably in a homogeneous or heterogeneous solvent phase, for example, acetone +water, dioxane-l-water or dimethylformamide, with cooling or heating, preferably at a temperature ranging from -30 to C.

If, in selecting a starting compound of the Formula III it is desired to carry out a selective substitution of the group X, a method known for the stepwise substitution in 1,3,5-triazines is employed (cf. Smolin et al., s-Triazines and Derivatives; Interscience Publishers, New York [1959]).

Another process for the manufacture of the active substances of the Formula I comprises reacting a compound of the formula l N N N wherein R and R have the above meanings and Y stands for a hydrazino group, with nitrous acid or a nitrous acid donor. Particularly suitable nitrous acid donors are the salts of this acid, and this reaction is carried out in an aqueous, acid solution.

Furthermore, there may be used for this purpose an alkylnitrite for example ethylnitrite, butylnitrite or amylnitrite in an alcoholic solution.

The present invention further includes the use of the compounds of the above Formula I for combating pests, especially undesired plant growth, and harmful microorganisms for example bacteria and fungi, insects, for example Musca domestica, acarides for example spinner mites, nematodes and molluscs, for example land and water snails.

The invention further includes the use of the compounds of the above Formula I for defoliating cotton plants.

It is a special advantage of the active substances of the above Formula I and of the preparations containing these active substances that they may be used not only as total herbicides but, when used in a suitable concentration, also as selective herbicides. Thus, it is possible, for example, to combat successfully undesired plant growth in cultures of useful plants without appreciably damaging the latter.

The preparations of this invention may be applied in a wide variety of forms. For manufacturing solutions of compounds of the general Formula I for direct spraying there may be used, for example, petroleum fractions of a medium to high boiling range, preferably above 100 C. for example Diesel oil or kerosene, coal tar oils and oils of vegetable or animal origin, also hydrocarbons for example akylated naphthalenes, tetrahydronaphthalene, if desired in combination with xylene mixtures, cyclohexanols, ketones, also chlorinated hydrocarbons for example trichloroethane, tetrachloroethane, trichloroethylene, trichlorobenzenes or tetrachlorobenzenes.

Aqueous forms of application are prepared, for example, by adding water to emulsion concentrates, pastes or wettable spray powders. Suitable emulsifiers or dispersants are, for example, nonionic products, such as condensation products of ethylene oxide with aliphatic alcohol amines or carboxylic acid containing a long chain hydrocarbon radical with about to carbon atoms, for example the condensation product of octadecyl alcohol with to mols of ethylene oxide, or of soybean fatty acid with 30 mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide. As examples of suitable anionic emulsifiers there may be mentioned the sodium salt of the dodecyl alcohol sulfuric acid ester, the sodium salt of the dodecylbenzenesulfonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these two acids, or the sodium salt of a petroleumsulfonic acid. Suitable cationic dispersants are quaternary ammonium compounds for example cetyl pyridinium bromide and dihydroxye-thyl benzyl dodecyl ammonium chloride.

Dusting and casting preparations may contain as solid vehicles talcum, kaolin, bentonite, calcium carbonate or calcium phosphate, also coal, cork meal, wood meal and other materials of vegetable origin. It is also very adv-antageous to manufacture the preparations as granules. The diverse forms of applications may contain the usual substances capable of improving the distribution, the adhesion, the stability towards rain or the penetration; as such substances there may be mentioned fatty acids, resins, glue, casein and alginates.

The preparations of the invention may be used by themselves or in combination with conventional pesticides, especially insecticides, acaricides, nematocides, bactericides or further fungicides and/or herbicides.

Weeds that can be controlled with the preparations of this invention include also undesired culture plants, for example such as have been planted previously on the soil to be treated. The preparations may be used both by the pre-emergence and the post-emergence method.

The compounds of the general Formula I are also suitable for use as polymerization accelerators in the manufacture of synthetic resins, for example styrene radicals.

The present invention further includes the new compounds of the general Formula I as such as well as their manufacture.

The following examples illustrate the invention. Unless otherwise indicated, parts and percentages in the above description and in the following examples are by weight.

Example 1 (1) 2-ethylamino-4-azido-6-chloro-1,3,5-triazine A solution of 12 parts of sodium azide in 100 parts of water wa mixed dropwise with a solution of 19.6 parts of 2-ethylamin0-4,6-dichloro 1,3,5-triazine in parts by volume of acetone while stirring vigorously, with the temperature of the suspension rising to 31 C. The mixture was stirred for 1 hour at this temperature and then filtered. The product was crystallized from alcohol; it melted at 97 to 98 C. The following compounds were manufactured in an analogou manner:

(2) Z-azido-4-n-butylamino-6-chloro-1,3,5-triazine, melting at 76 to 77 C., from alcohol,

(3) 2-axido-4-chloro-6-isobutylamino-1,3,5-triazine, melt ing at 110 to 111 C., from cyclohexane, and

(4) 2-azido-4-secondary butylamino-6-chloro 1,3,5-triazine, melting at 48 to 52 C., from hexane.

The 2,4-dichloro-6-secondary butylamino 1,3,5-triazine required as intermediate for the manufacture of compound No. 4 was prepared as described by J. T. Thurston et al., in I. Am. Chem. Soc. 73 page 2981 [1951]. The product was extracted from the reaction mi ture with chloroform and then distilled; it boils at 108 to 110 C. under 0.07 mm. Hg pressure.

(5) 2-azido-4-tertiary butylamino-6-chloro-1,3,5-triazine,

melting at 7376 C. (hexane) (6) 2-azido-4-fluoro-6-isobutylamino-1,3,5-triazine While cooling a mixture of 135 parts of cyanuric fluoride and 1000 parts by volume of acetone with ice, 147 parts of isobutylarnine were dropped in. On completion of the reaction the mixture was filtered, and the filtration evaporated, the residue taken up in 500 parts by volume of toluene and washed with ice water. The solution was dried with anhydrous SOdllll'ill sulfate and evaporated. The resulting 2,4-d-iflnoro-6-isobutylamino-1,3,5- t-riazine was distilled under a high vacuum; it boiled at to 92 C. under 0.2 mm. Hg pressure and melted at 41 to 43 C.

26 parts of 2,4-difiuoro-6-isobutylamino-1,3,5-triazine were dissolved in 50 parts by volume of acetone and 10 parts of sodium azide and 10 parts of water were stirred in, while maintaining the temperature below 32 C. by cooling. The mixture wa then stirred for 24 hours at room temperature, mixed with 200 parts of water, the precipitate formed was filtered off, dried and repeatedly recrystallized from hexane and cyclohexane. It melted at to 103 C.

(7) 2-azido-4-bromo-6-isobutylamino-I1,3,5-triazine 57.5 parts of isobutylamine were added dropwise at 0 C. to a suspension of parts of cyanuric bromide in 400 parts by volume of acetone, and the mixture was then stirred for 4 hours at room temperature, filtered and the filtrate was evaporated. The residue was dissolved in 750 parts by volume of toluene and washed with ice water. The solution was dried over anhydrous sodium sulfate and evaporated. The resulting 2,4-dibromo-6- isobutylamino-1,3,5-triazine was crystallized from cyclohexane; it melted at 92 to 94 C.

46.5 parts of 2,4-dibromo-6-isobutylamino-1,3,5-triazine were dissolved in 60 parts by volume of acetone and 10 parts of sodium azide and 20 parts of water were stirred in. The mixture heated up to 41 C. and was then stirred for 24 hours at room temperature. The product was taken up in 200 parts by volume of toluene and washed with 2 100 parts of water. The solution was evaporated. The resulting 2-azido-4-bromo-6-isobutylamino-1,3,5-triazine was crystallized from petroleum ether; it melted at 83 to 87 C (8) 2-amido-4-isopropylamino-6-methyl-1,3,5-triazine A solution of 41 parts of 2,4-dichloro-6-methyl-1,3,5- triazine in 400 parts by volume of acetone was mixed dropwise with 30 parts of isopropylaniine, while cooling to maintain the temperature at about 25 C. The mixture was then further stirred for 5 hours at room temperature, filtered and evaporated. The residue was dissolved in 300 parts by volume of hexane. The solution was washed with ice water, dried over anhydrous sodium sulfate, filtered and evaporated. The resulting 2-chloro-4- isopropylamino-6-methyl-l,3,5-triazine was distilled; it boiled at 143 to 146 C. under 16 mm. Hg pressure and melted at 45 to 47 C.

A solution of 34.5 parts of 2-chloro-4-isopropylamino- 6-methyl-1,3,5-triazine in 700 parts by volume of dry toluene was mixed at about 5 C. with 100 parts by volume of 4-molar toluolic trimethylamine solution. The mixture was kept for a few hours at 5 C. and then for 2 days at room temperature. The precipitated quaternary ammonium salt was filtered off and dried in a high vacuum at room temperature.

A solution of 24.6 parts of 6-(2-isopropylamino-4- methyl-1,3,5-triazinyl)-trimethyl ammonium chloride in X N F R1\\N)NI'IR2 R1= R2= X=Cl; 111.1%, O. X=N3; M.l., C.

(15) Methylmereapto Sec. butyl 39-42" (13.1. 122, 0.5 mm. Hg) (SQ-71, petroleum ether. (16) do fl-Methoxyethyl 8587, hexane 90, methanol.

"3 BM in 1m v t thyl i iig l i i o e y eieap oe yeo xane. a com (19) Isopropylmereapto -Methoxypropyl 72-743: hexane"... 74-75 methanol. (20) n-Butylmereapto ..d0. GEE-65 cyelohexana. 34 36 hexane. (21) See. butylmereapto do 58450 petroleum etli 52-53", petroleum ether.

50 parts of water was mixed with 12 parts of sodium azide, and the mixture stirred for 3 hours at 50 C. and allowed to cool. The precipitate was filtered off, washed with water, dried and crystallized from hexane. It melted at 71-72 C.

(9) 2-ethylamino-4-azido-6-methylmercapto-1,3,5-triazine A solution of 39.9 parts of 2,4-dichloro-6-methylmercapto-1,3,5-triazine in 120 parts by volume of dioxane was vigorously stirred dropwise at about C. into a mixture of 13 parts of ethylamine of 70% strength and 200 parts of water. 100 parts by volume of 2 N-sodium hydroxide solution were then added portion-wise and the temperature allowed to rise to C. When the sodium hydroxide solution was consumed, 20 parts of solid sodium azide were added and the emulsion stirred for 6 hours at about 75 C. The mixture was then cooled. The precipitated product was filtered off and washed with 2x100 parts of water, then crystallized from methanol, whereupon it melted at 114 to 116 C.

In an analogous manner the following compounds were manufactured from 2,4-dichloro-6-methylmercapto-1,3,5- triazine and the corresponding amines:

(10) 2 azido 4 methylamino--methylmercapto-1,3,5- triazine, melting at 164 to 165 C., from alcohol (11) 2-azido 4 methylmercapto-6-n-propylamino-1,3,5-

triazine, melting at 104 to 105 C., from methanol (12) 2 azido-4-isopropylamino-6-methylmercapto-1,3,5-

triazine, melting at 92 to 94 C., from cyclohexane (13) 2-azido-4-n-butylamino 6 methylmercapto-1,3,5- triazine, melting at 93 to 95 C., from methanol (14) 2 azido-isobutylamino-6-methylmercapto-1,3,5-triazme A solution of 196 parts of 2,4-dichloro--methylmercapto-1,3,5-triazine in 1000 parts by volume of benzene was mixed drop-wise with 146 parts of isobutylamine, while cooling externally to maintain a temperature below 20 C. The mixture was then stirred at room temperature until no more free amine could be identified and filtered. The filtrate was washed with ice water, dried over anhydrous sodium sulfate and evaporated, the residue being crystallized from hexane. The resulting 2 chloro 4 isobutylamino-6-methylmercapto-1,3,5-triazine melted at 109 to 111 C.

A mixture of parts of 2-chloro-4-isobutylamino- 6-methylmercapto-1,3,5-triazine, parts of sodium azide, 150 parts by volume of dioxane and 150 parts by volume of water was stirred for 24 hours at 80 C. The product was extracted with 300 parts by volume of toluene. The extract was washed with 2x100 parts of water, dried over anhydrous sodium sulfate and evaporated. The resulting 2-azido-4-isobutylamino-6-methylmercapto-1,3,5- triazine melted at 102 to 103 C., and after crystallization from cyclohexane at 102 to 104 C.

In an analogous manner, the compounds listed in the (22) In the same manner, using as starting material 2,4- dichloro-6-methylmercapto-1,3,5-triazine, there was obtained via the intermediately formed 2-chloro-4-diethylamino-6-methylmercapto 1,3,5-triazine (from petroleum ether, M.P. 5355 C.) the 2-azido-4-diethylamino-6-methylmercapto-l,3,5-triazine; this compound was liquid and displayed in the infrared spectrum a strong band at 4.66 4.

(a) 2-secondary butylmercapto-4-chloro-6-isopropylamino-1,3 ,5 -triazine (b) 6-(2-secondary butylmercapto-4-isopropylaminotriazinyl)-trimethyl ammonium chloride A solution of 78 parts of 2-secondary butylmercapto-4- chloro-6-isopropylamino-1,3,5-triazine in anhydrous toluene was stirred dropwise at -5 to 0 C. into a solution of parts of trimethylamine in 500 parts by volume of anhydrous toluene, whereupon the mixture was further stirred for 14 hours at about 20 C. The resulting quaternary salt was filtered off, washed with toluene and dried in a high vacuum at room temperature.

(c) 2-azido-4-secondary butylmercapto-6-isopropylamino- 1,3,5-triazine 20 parts of 6-(2-secondary butylmercapto-4-is'opropylamino-triazinyl)-trimethyl ammonium chloride were dissolved at room temperature in 50 parts of water, 17 parts of solid sodium azide were stirred in and the whole was heated for a short time at about C. Parts by volume of benzene and 100 parts of water were then added, the aqueous phase was sepaarted and the benzolic solution dried over anhydrous sodium sulfate, filtered and evaporated. The residue was freed in a high vacuum at room temperature from the last remanents of solvent, to yield pure 2-azido-4-secondary butylmercapto-6-isopropylamino-1,3,5-triazine as a viscous oil.

In an analogous manner, using as starting materials 2- alkylmercapto 4,6 dichl'oro 1,3,5-triazines, the following compounds were manufactured (the compounds obtained in crystalline form on reaction with sodium azide were filtered off, washed with water, dried and recrystallized).

X A N N CHaSk J-NH-R R= X=C1; M.P., C. X=Na; M.P., C.

(24) Tert. butyl B.P. 9798, 0.02 mm. Hg 59-03", petroleum ether. (25) Octadecyl- 58-60", hexane 79-80", methanol. (20) Oleyl Liquid Liquid. (27) Cyclopropyl 105407", toluene 107108. (28) Oyolopentyl 42-44 (13.1. 140-145" 0., 76.

0.05 mm. Hg). 110-111, cyelohexane.. 12-113", methanol.

.. Cyelododecyl 8 (or 9) tetrahydroexo-dicyolopentadienyl.

(33) fi-Hydroxyethyl 125-126", nitrobenzene 105-109", methanol.

(34). [3,5-dimethoxyethyl. 90-91", cyelohexane 88, methanol.

(35)... fl-Cyanoethyl 133-134 146148, aqueous methanol. (36)... 'y-Methoxypropyl 68-69", cyclohexane Identical with (17).

R R2: X=Cl; M.P., C. X=N3; M.P C

(37) Ethyl Isopropyl (B.P. 128, 0.06 mm. Hg). uid. (38) Isopropyl Isobutyl 97-99, hexane 106-107, methanol. (39) do Secondary butyl (13.1. 124, 0.3 mm. Hg) Liqu (40)... n-Butyl. Isopropyl (13.1. 123, 0.1 mm. Hg) 27-33".

Isobutyl... 58-59", hexane (SO-61, methanol. (1 Sec. butyl (B.P. 158-160, 0.6 mm. Hg)-.. Liquid. Isobuty Isopropyl... (B.P. 130, 0.15 mm. Hg.... Do. (44) ..do Isobutyl. (B.P. 143145, 0.2 mm. Hg); 65-66", methanol.

M.P. 45-47". (45) --do. Sec. butyl (B.P. 135, 0.2mm H Liquid. (46) ..do 'y-methoxypropyl 4647 (3.1).. 168-169", 0.1 4748", aqueous methanol.

mm. g (47) Sec. butyl. Isopropyl 127-128", 0.04 mm. Hg Liquid. (48) Isoamyl Isobutyl 74-76", hexane (iii-68, methanol.

(49) 2-azido-4-methylmercapto 6 piperidino 1,3,5- triazine melting at 70 to 72 C., methanol, from 2- chloro-4-methylmercapto-6-piperidino 1,3,5 triazine, melting at 81 C., hexane.

(50) 2-azido-4-rnethylmercapto 6 morpholino 1,3,5- triazine melting at 98 to 99 C., methanol, from 2- chloro-4-methylmercapto-6-morpholino-1,3,5 triazine, melting at 92 C. from cyclohexane.

(a) 2-ethylamino-4-hydrazino-6-methylmercapto- 1,3,5-triazine 10.5 parts of hydrazine hydrate and then 8 parts of sodium hydroxide, dissolved in 20 parts of water, were added dropwise at 30 to 50 C. to a solution of 41 parts of Z-ethylamino-4-chloro-6-methylmercapto-1,3,5-triazine in 200 parts by volume of dioxane. The mixture was heated for several hours at 55 C. and then poured into 600 parts of ice water. The crystalline product was filtered off, washed with ice water and twice recrystallized from alcohol; it melted at 150 to 151 C.

(b) 2-ethylamino-4-azido-o-methylmercapto-1,3,5-triazine (52) 2-azido-4-ethylamino-6-methoxy-1,3,5-triazine A solution of 84 parts of 2,4-dichloro-6-methoxy-1,3,5-

triazine in 700 parts by volume of toluene was mixed at 5 to 8 C. dropwise with 62 parts of ethylamine of 70% strength. When the mixture gave a neutral reaction, 300 parts of water were added. The organic phase was separated, dried over anhydrous sodium sulfate and evaporated. The residue-2 ethylamino 4 chloro-6-methoxy- 1,3,5-triazine-was crystallized from hexane and melted at 96 to 98 C.

A mixture of 38 parts of 2 ethylamino 4 chloro-6- methoxy-1,3,5-triazine, 50 parts of sodium azide, 150 parts by volume of dioxane and 150 parts of water was stirred for 48 hours at 60 C. 200 Parts of water were then added at room temperature, the crystalline product was filtered off and crystallized from methanol; it melted at 116 to 117 C.

The following compounds were manufactured in a similar manner:

(53) 2-azido-4-ethoxy-6-ethylamino-1,3,5-triazine, melting at 98 to 99 from cyclohexane, from 2-ethoxy-4- ethylamino-4-chloro-1,3,5-triazine melting at to 91 C., from hexane.

(54) 2-azido-4-isopropylamino-G-methoxy-1,3,5-triazine A stirred solution of 270 parts of 2.4 dichloro 6- methoxy-1,3,5-triazine in 1500 parts by volume of toluene was mixed dropwise with 89 parts of isopropylamine and then with 360 parts of sodium hydroxide solution (prepared from 60 parts of sodium hydroxide and 300 parts of water). By cooling with ice the temperature was maintained below 20 C. The mixture was then stirred at about 20 C. until a neutral reaction materialized. The organic phase was separated, dried over anhydrous sodium sulfate, filtered and evaporated. The residue was crystallized from hexane and melted at 65 to 66 C.; it was 2-chloro-4- isopropylamino-6-methoxy-1,3,5-triazine.

A solution of 101 parts of 2-chloro-4-isopropylamino-G- methoxy-1,3,5-triazine in 1500 parts by volume of anhydrous toluene was mixed at +5 C. dropwise with 175 parts of a 4-molar toluol solution of trimethylamine. The mixture was then kept for about 14 hours at room temperature. The precipitated quaternary salt was filtered off, washed with anhydrous toluene and dried in a high vacuum at room temperature.

lar manner hydrazino-6-methoxy-1,3,5-triazine.

turned blue by a specimen.

6) d (57) .do 58) do (59) do.. (60) (lo.

. 53-55 (Bl 114-116", 0.1 mm. Hg)

98-99, hexane (13.1. 109-112, 0.3 1nm.llg)......

64-65 hexane 73-74", aqueous methanol.

73-74 hexane 102-103", methanol.

63-64, hexane (61) .do 11., 5-dimethylpentyl. (15.1. 138-140, 0.3 mm. Hg) Liquid, highly viscous. (62).. ..do.. Cyclohexyl. 100-101", eyclohexane 131-132, methanol. (63) n-lropyL. Methyl 103-104, cyclohexane 92-94 methanol. (64) ..(l Ethyl.... (54-65" (13.1. (S-120, 0.2 mm. Hg). 76-77 methanol, (65) 0.. n-Propyl... 51-55 (13.1. 132-135, 0.25 mm. Hg). til-63 methanol. (66).. Isopropyl 13.1. 124-128, 0.45 mm. Hg 96-97 n'iethanol. (67 Isobutyl. 15.1. Mil-150, 0.5 mm. Hg... 77-78", methanol. (08)-. 13.1. 130-133, 0.45 mm. Hg... 40-41", methanol. (69 13.1. 118123 0.45 mm. Hg... Liquid, highly viscous. (70). 80-81", hexane 83-85", methanol (71).. nPropyl 7172. hexane 73-75", methanol (72).. Isopropyl 85-86 hexane 57-58", methanol. (73).. 73-75 hexane... 64-65, methanol. (74).. 93-95 hexane 99-100, methanol. (75). 66-68 hexane 91-92, methanol. (76).. 63-64 ,hexane..... 0-71, methanol. (77).. 49-51 (13.1. 142. 0. 5859 methanol. (78).. (13.1. 107-110, 0.2 mm. Hg).. 62-63 methanol. (79). 4243 (13.1. 121-128, 0.2 mm 62-63, methanol. (80). (B.P. 128132, 0.1 mm. Hg).. 64-65, methanol. (81). (B.P. 118-120, 0.2 mm. Hg).. 47-48, methanol. (82). 65-68" (B.P. 122-124 0.2 mm. Hg)... 69-70", methanol. (83). 39-41 (B.1. 132-135 0.07 mm. Hg)... 54-55", methanol. (84). (iii-67 (13.1. 132-135" 0.28 mm. Hg) 64-65", methanol. (85). 4546 (B.P. 148-152 0.5 mm. Hg) 7677, methanol. (86). 50-52" (B.P. 140, 0.3 mm. Hg)........ 61-62, methanol. (87). (B.P. 134-136", 0.35 mm. Hg) Liquid (88). 6465 (15.1. 132-135, 0.3 mm. Hg) 70-72 methanol (89). Sec. butyl. (13.1. 117-119, 0.1 mm. Hg) 59-60 ,methanol. (90). Isopropyl (13.1. 121, 0.04 mm. Hg) 78-80", methanol.

(91) 2 azido 4-dimethylamino-6-isopropoxy-1,3,5-triazine melting at 80 to 82 C. (methanol) from 2- chloro-44iimethylamino-6-isopropoxy 1,

melting at to 107 C. (hexane).

(92) 2 azido 4 cyclohexylamino-6-methoxy-1,3,5-triazine it melted at 94 to 95 C.

3,5 triazine proportion of free amine remained. 75

rated. The residue was amorphous 2-cyclohexy1amino-4- 23.8 parts of crude 2-cyclohexylamino-4-hydrazino-6- methoxy-1,3,5-triazine were dissolved in 220 parts of about normal hydrochloric acid. At about 0 C. a solution of 6.9 parts of sodium nitrite in 50 parts of water was added dropwise until potassium iodide-starch paper was The precipitated product was filtered off, washed with water and crystallized from methanol; it was identical with 10 the compound obtained as described under 62.

(93) 2-ethylamino-4,6-diazido-1,3,5-triazine A solution of 18.4 parts of cyanuric chloride in 70 parts 15 by volume of acetone was added dropwise, while being well stirred, to a solution of 20 parts of sodium azide in 125 parts of water at 0 to 5 C., whereupon the mixture was stirred for a short time. A specimen of the crystal- 63-64, aqueous methanol. 67-60 aqueous methanol. aqueous methanol. 55-56 ,hexane line product was filtered off and crystallized from alcohol;

The resulting dispersion of 2-chloro-4,6-diazido-1,3,5- triazine was dissolved in 200 parts by volume of toluene; this solution was mixed with 6.8 parts of aqueous ethylamine of 70% strength and stirred at 40 to 50 C. During 30 minutes, 50' parts of 2 N-sodium hydroxide solution were stirred in portionwise at 40 to 50 C., and the batch was allowed to cool, while being stirred. The organic phase was separated, dried over anhydrous sodium sulfate, filtered and evaporated. The residue was crystallized from methanol or cyclohexane; it melted at 122 to Instead of sodium hydroxide solution, there could have been used an equivalent quantity of ethyla'mino as hydrochloric acid acceptors; in this case the batch would have been allowed to react at 40 C., until only a small The Z-alkylamino-4,6-diazido-1,3,5-triazines listed in azine, 15 parts of sodium azide, 75 parts by volume of acetone and 50 parts of water were stirred for 24 hours NHR at 60 C. The mixture was then mixed with 200 parts of water. The crystalline product was filtered off, washed With water and crystallized from acetone; it melted at 117 N to 118 c. l J As described above, 196 parts each. of 2,4-dichloro-6- N methylmercapto-1,3,5-triazine were reacted with the following amounts of mercaptans and alcohols: R= Melting at-( C.) 10 Parts E33 "1:: fiii lifiaii 11:11:: i i fetif fiiiif Isobutylmercaptan 140 (96) Isopropyl- 123-124: (methanol). Methanol 50 E38 msikt 'tjii3311111313331: ii ii EESEEZESBI lsobutanol 100 (99). Isobutyl. c 1l5-116 (methanol). 88% ife gg l l yln ggj g pfig gg ethel) 15 The resulting 2-alkylmercaptoand 2-alkoxy-4-methyl- (10 %i fi j (methanof) rnercapto6-chlorotriazines respectively were reacted With f yp pyligft lg gmethg ollsodium azide as described above to give rise to the fol1owyclo e e mg compounds i W 01133 N J R R= X=o1; M.P., 0. X=Na; M.P., o.

(111) Isobutylmercapto 13.1. 128-130", 0.4 mm. Hg Liquid. (112) Mcthoxy r. 7677(B.P.125l28,0.5mm. Hg). 70-7 ,methanol. (113) Isobutoxy 2830 (B.P.135137,1.5mm.Hg) Liquid.

Further manufactured were the following compounds: (114) 2,4- diazido-6-methoxy-1,3,5triazine 105 2-diethylamino-4,6-diazido-1,3,5-triazine, melting at of 36 P of 2,4-dlcflloro-fi-methoxy-1,3,5-

to O Cy c1 (hexane). o tr azine in 70 ml. of dioxane was stirred dropwise at about (106) 2 4 djaZidOA6 m0rphO1ino mgmriazine, melting at 0 C. 1nto 39 parts of sodium azide lIl l50 parts of water,

a o and the mixture was then stirred for minutes at about zi ig gliziggffifi 3 20 C. The oil which had settled out was taken up in 200 s triazine parts by volume of benzene, dried and filtered. The filtrate was evaporated in a Water-jet vacuum at room temperature 2,4 dichlorosg-(fimethylmercapto-ethylamino)4,3,5. and diluted with 100 parts by volume oi methanol. The triazine can be prepared by the method of I. T. Thurston Product, meltfng at to cfystfllllled Q p et aL (J. Amer Chem 73, page 29 1 19 3 f The followmg compound was manufactured in a simllar cyanuric chloride and [3-methyl-mercapto-ethylamine. It f f from 2,4 dlchloro 6 methylmel'capto melts at 75 to 77 C. (from xylene+cyclohexane). trlazme:

3 parts o -(fi-m 115 2,4 diazido 6 methylmercapto-1,3,5-triazine a o)-1,3,5-tnaz1ne weremrxedwlth 60 parts by v lu which can be crystallized from cyclohexane and melts of acetone, 30 parts of sodlum azide and 30 parts of Water at and the whole was stirred for 24 hours at 6 0 C. and then allowed to cool, whereupon 100 parts of water were added. 5 (116) 2,4-diazido-6-isobutoxy-1,3,5triazine The crystalline product was filtered off, washed with water A mixture of 20 parts of 2 4 dichloro 6 isobutoxy 1,3,5 and crystallized from methanol; it melted at 95 to 96 C. triazine 20 parts of sodium azide and parts by Volume of acetone was stirred and mixed with 50 parts of Water, (108) .In an analogous manner 2,4-diaZido-6-sec-butyl whereupon the batch spontaneously heated up to 60 C. aminO-1,3.5-triazine was p p from A- The mixture was then further stirred for 14 hours at room 6-sec'butylamino-1,3,5-triazine. The product crystaltemperature.

lized at a low temperature. The product was taken up in 100 parts by volume of (109) In an a og manner y toluene and washed twice with water. The solution was 1=3,5"[FiaZiI1e yielded y evaporated under vacuum at a maximum temperature of azine: it is identical with the product No. 93, obtained 50 C The id was pure liquid g 4 i b from 2,4-diazido-6-chloro-1,3,5-triazine and ethylamine. tQXy-1,3 5 tfiaZine Y P t In a similar manner the following diazides, which are liquid at room temperature, were manufactured from the A 0 of 75 Parts of methylmel'captan and 107 Parts corresponding 2-alkoxyand 2-alkoxymercapto-4,6-dichl0- of 2,6-lut1d1ne was added portionwise at 0 to 5 C. to a m4 3,54riazines: solution of 196 parts of 2,4-dichlor0-6-methy1mercapto- 1,3,5-triazine in 1000 parts by volume of acetone. The mixture was kept for 2 hours at room temperature, then \\I for 14 hours at 50 C., filtered and evaporated. The residue N was taken up in 1000 parts by volume of toluene, washed l l with 2x 150 parts of ice water, dried over anhydrous W- sodium sulfate, filtered and evaporated. The resulting crude 2 chloro-4,6-dimethylmercapto-1,3,5-triazine was crystallized from hexane and melted at 84 to 86 C. (117) n-propoxy 21 parts of 2 chloro-4,6-dimethyl-mercapto-1,3,5-tri- (118) isopropoxy Manufacturing the 2,4-dichloro-6-(2-methyl-A '-cyclohexenyl-methyloxy)-1,3,5-triazine required for making the compound No. 125.

A mixture of 200 parts of 2methyl-M-cyclohexenylmethanol and 107 parts of 2,6-lutidine was dropped at C. into a solution of 184 parts of cyanuric chloride in 1000 parts by volume of acetone. The mixture was heated for 14 hours at 50 C., then cooled, filtered and evaporated. The residue was dissolved in toluene and washed with ice water. The solution was dried over anhydrous sodium sulfate and evaporated. The liquid product was dis tilled. It boiled at about 140 C. under a pressure of 0.2 mm. Hg.

allyloxy propargyloxy 'y-chloropropoxy n-butoxy n-octyloxy cyclohexyloxy Z-methyl-A -cyclohexenyl-methyloxy n-propylmercapto isopropylmercapto n-b utylmercapto isobutylmercapto allylmercapto Example 2 In each experiment, 10 parts of one of the compounds of Example 1 were mixed With 20 parts of dimethylformamide and 10 parts of a condensation product from an anionic surface-active compound (preferably the calcium or magnesium salt of monolauryl benzene monosulfonic acid) with a nonionic surface-active compound (preferably a polyethyleneglycol ether of the monolauryl ester of sorbic acid) and then diluted with Xylene to 100 cc. The resulting clear solution was suitable for use as a spray broth concentrate and could be emulsified by being poured into water.

Example 3 A. In a greenhouse, earthenware pots were filled with earth and the following plants were seeded in them: Avena sativa, Setaria italica, Sinapis arvensis and Lepia'z'um sativum.

The pre-emergence treatment was carried out 1 day after seeding with spray broths prepared according to Example 2, which contained as active substance the compound No. 9 of Example 1. The amount applied corresponded to 10 kg. of active substance per hectare. Evaluation of the results was carried out 20 days after the treatment.

The post-emergence treatment of the plants mentioned above was carried out in a similar manner, but only 10 days after seeding, when 2 to 3 leaves had appeared.

The amount applied corresponded to 5 kg. of active substance per hectare. Evaluation of the results was carried out 20 days after the treatment. The results are summarized in the following table.

TABLE Pre- Post- Plant tested emergence emergence treatment treatment Arena sativa 1O Setaria italica. 9 10 Sinapis arvensis. 10 9 Lepidium sativu 10 10 The post-emergence treatment of the plants mentioned was carried out in identical manner, but only 10 days after seeding when 2 to 3 leaves had appeared. The amount applied corresponded to 4 kg. of active substances per hectare. Evaluation was carried out 20 days after the treatment. The results are summarized in the following.

TABLE Pre- Post- Plant tested emergence emergence treatment treatment 'lriticum 9 9 Hordeum 10 8 Sorghum sudanense. 9 9 Panicum crus galli 10 10 Poa trivialis 10 10 Dactylis glomerata" 10 10 Allium cepa 1O 10 Beat vulgaris 10 10 C'alemiula chrysantha. 10 10 Linum usitatissimum 10 10 Bmssz'ca rape 10 10 Daucus carotm... 10 10 Lactuca sativa. 10 10 Medicago sativa 10 10 Soja. max... 8 10 Phaseolus vulgaris 7 9 where 0 indicates no effect, 10 means plants completely destroyed.

Under the test conditions described under (A) and (B), good to very good herbicidal effects were obtained with the compounds Nos. 1, 3, 4, 5, 9, 11, 13 to 17, 24, 53, 54, 96, 98 to 101, 104, and 115 of Example 1.

When used for the post-emergence treatment, a selective action against dicotyledons was observed, for example, with the compounds Nos. 26 to 129 of Example 1.

Example 4 The compounds Nos. 1, 3, 10 and 115 of Example 1 displayed a good microbicidal effect, for example against phytopathogenic fungi. Thus, in a concentration of 0.2% of active substance a 100% effect against Septoria apii on celery was recorded, and the plants treated did not suffer any appreciable damage.

Example 5 2 parts of the following compounds were dissolved in 100 parts each of freshly distilled styrene:

2,4-diazido-6-n-propoxy-1,3,5-triazine, 2,4-diazido-6-n-propylmercapto-1,3,5-triazine and 2-ethylamino-4,6-diazido-1,3,5-triazine.

A fourth styrene specimen was not given any additive. All test specimens were maintained at C. After 4 hours and 15 minutes the mixtures containing one of the above compounds had solidified to jellies, whereas the blank test specimen was still liquid.

What is claimed is:

1. A compound of the formula Na l wherein R represents a member selected from the group consisting of a lower :alkyl radical and the radical ZX, wherein Z represents a member selected from the group consisting of oxygen and sulfur, and X represents a member selected from the group consisting of an aliphatic hydrocarbon radical containing up to 8 carbon atoms, a lower alkoxyalkyl radical, a lower chloroalkyl radical, a cyclohexyl radical, a cyclohexyl radical substituted by a lower alkylene group and a lower alkyl group, R represents a member selected from the group consisting of (a) a halogen atom, (b) a radical as defined above in the case of R (c) the azide radical, (d) the radical wherein X represents a member selected from the group consisting of an alkyl radical and an alkenyl radical containing up to 5 carbon atoms, and R represents a member selected from the group consisting of the group wherein A represents a member selected from the group consisting of an alkyl radical and an alkenyl radical containing up to 18 carbon atoms, a 3- to l2-membered cycloaliphatic radical, a lower alkoxyalkyl, hydroxyalkyl, cyanoalkyl and alkylthi oalkyl radical, A represents a member selected from the group consisting of a hydrogen atom, and a lower alkyl radical and A together with A represents a member selected from the group consisting of the piperidino and morpholino radical; an amide radical, a lower alkoxy radical, a halogen atom and the radical as defined above for SX.

3. A compound of the formula R LNJ OX (V) wherein X represents a member selected from the group consisting of saturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, an unsaturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, a lower alkoxyalkyl, a chloralkyl radical, a cyclohexyl radical and an alkylene-cyclohexyl-alkyl radical, and R represents a member selected from the group consisting of the azide radical and the group 18 wherein A stands for a saturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, an unsaturated aliphatic hydrocarbon radical containing up to 8 carbon atoms, a lower alkoxyalkyl radical and a cyclohexyl radical, and A represents a member selected from the group consisting of a hydrogen atom and a lower alkyl radical.

4. A compound of the formula N X-l NH-R N v1 wherein R represents a member selected from the group consisting of lower alkyl, -a lower alkoxyalkyl and cyclohexyl group, and X represents a member selected from the group consisting of a chlorine atom, CH S, CH O, and the azide radical.

5. The compound of the formula N N on,

CH3 6. The compound of the formula N N CH3 References Cited UNITED STATES PATENTS 2,211,709 8/ 1940 Zeweck et a1. 260249.8 2,267,068 12/ 1941 Zeweck et al. 260249.8 3,321,453 5/1967 Breslow 260249.8

JOHN D. RANDOLPH, Primary Examiner. J. M. FORD, Assistant Examiner.

U.S. Cl. X.R. 260-249.9, 249.5, 247.5, 249.6, 93.5; 167-33; 71-93 

